DEFINITION OF HAZARDOUS MATERIALS

Hazardous materials, as discussed in this course, may be defined as:

A substance or material that the Secretary of Transportation has determined is capable of posing
an unreasonable risk to health, safety, and property when transported in commerce. The term
includes hazardous substances, hazardous wastes, marine pollutants, elevated temperature
materials, materials designated as hazardous in the Hazardous Materials Table,
and materials that meet the defining criteria for hazard classes and divisions in the
standard.

Substances or materials, which because of their chemical, physical, or biological nature, pose a
potential risk to life, health, or property if they are released.
A release may occur by spilling, leaking, emitting toxic vapors, or any other process that
enables the material to escape its container, enter the environment, and create a potential hazard.
Hazards are classified in many different ways. The following introduces several common terms:

1. Explosive substances release pressure, gas, and heat suddenly when they are subjected to
shock, heat, or high pressure. Fourth of July celebrations use many types of explosive
substances that require careful storage and handling to avoid injury.

2. Flammable and combustible substances are easy to ignite. Paint thinners, charcoal lighter
fluid, and silver polish are all highly flammable. Oxidizers, which will lend oxygen readily to
support a fire, and reactive materials, which are unstable and may react violently if
mishandled, pose related hazards.

3. Poisons (or toxic materials) can cause injury or death when they enter the bodies of living
things. Such substances can be classified by chemical nature (for example, heavy metals and
cyanides) or by toxic action (such as irritants, which inflame living tissue, and corrosives,
which destroy or irreversibly change it). One special group of poisons includes etiological
(biological) agents. These are live microorganisms, or toxins produced by these
microorganisms, that are capable of producing a disease.

4. Radioactive materials are a category of hazardous materials that release harmful radiation.
They are not addressed specifically in this course.
These categories are not mutually exclusive. For example, acids and bases are listed as corrosive
materials, but can also act as poisons.

HOW HAZARDOUS MATERIALS HARM THE BODY

Absorption and injection are two routes of entry that occur through direct skin contact with a
hazardous material.

Chemicals and hazardous substances may enter the body by several routes, and the nature and
onset of signs and symptoms may vary accordingly. Gases, vapors, and aerosols, when inhaled,
may be absorbed through any part of the respiratory tract, from the mucosa of the nose and
mouth to the alveoli of the lungs. The eye may also directly absorb them. Aerosol particles larger
than 5 micrometer (m) tend to be retained in the upper respiratory tract, while those smaller
than 1 m tend to be breathed in and out again, although some of these smaller particles may be
retained. Droplets of liquid and, less commonly, solid particles may be absorbed through the
surface of the skin and mucous membranes. Toxic compounds with a characteristic action on the
skin can produce their effects when deposited on the skin as solid or liquid particles.
Chemicals or hazardous substances which penetrate the skin may form temporary reservoirs so
that delayed absorption may occur. Even the vapor of some volatile chemicals and agents can
penetrate the intact skin and intoxication may follow. Wounds or abrasions (even minor injuries
caused by shaving or by chemical depilation) present areas which are more permeable than intact
skin. Chemicals and hazardous substances may contaminate food and drink and so be absorbed
by the gastrointestinal tract. The penetration of chemicals and hazardous substances by these
various routes may not be accompanied by irritation or damage to the surfaces concerned.

Methods of exposure to these chemicals are called routes of entry. They are:
1. Absorption
2. Ingestion
3. Injection
4. Inhalation

1. Absorption (through the skin or eye)

If a child were to walk barefoot through contaminated soil, the contaminant would contact
the skin of the foot. This could cause mild skin irritation, or more serious problems like
burns, sores, or ulcers on the outer layers of the skin. Contact with a substance may also
occur by spilling it on the skin or brushing against a contaminated object.

Depending on the substance and the condition of the skin, the contaminant might also be
absorbed through the skin and poison the body. While some chemicals are not absorbed
easily unless the skin is cut, others are absorbed quite readily regardless of the skins
condition. When you are using a material that bears instructions recommending the use of
gloves, this is to prevent skin contact or absorption through the skin (also called dermal
exposure).
When you work with chemicals, it is particularly important never to put your hand to your
eye. Eyes are particularly sensitive to toxic substances; since capillaries are near the surface,
the substance can enter the bloodstream more readily. Eye contact with toxic substances can
cause irritation, pain, or even blindness.

2. Injection
The most familiar example of injection is that of shots given to administer medicine, in
which the skin is punctured with needles so that a substance can enter the body. Injection can
also occur accidentally. For example, if a contaminated can or a piece of glass that had been
in contact with a contaminant cut the skin, the contaminated substance could be injected into
the body. This is a very powerful means of exposure because the contaminant enters the
bloodstream immediately.

When we ingest (eat) or inhale a substance, the body tries to filter it out through internal
defenses. If there is enough of the substance, these filters are overwhelmed.

3. Ingestion
If we eat a substance that contains a harmful material, that substance enters our bodies by
means of our digestive system. An example of inadvertent ingestion is a battery factory
employee who eats lunch in the work area and ingests inorganic lead that has contaminated a
sandwich. A more common instance is the child who puts a toxic substance in his or her
mouth out of curiosity. We may also ingest residue from chemicals that have been added to
our food to kill germs or parasites.

4. Inhalation
It is also possible to be contaminated by toxic substances when we breathe them into our
lungs. The amount of air inhaled in a workday can be extremely large, so if we work or live
in a contaminated area, we can be exposed to significant quantities of a substance in this way.
Some chemicals have excellent warning properties that let us know when they are in the
atmosphere. There is the well-known rotten egg smell of hydrogen sulfide, for example.
But at high concentrations of this gas, our sense of smell is quickly lost. Many toxic substances,
such as carbon monoxide, are both colorless and odorless, providing us with no sensory clues that
we are being exposed to anything unusual.

TOXIC MATERIALS IN THE BODY

A poison, or toxic substance, may be defined as a chemical that, in relatively small amounts,
produces injury when it comes in contact with susceptible tissue. Clearly, the phrase relatively
small amounts is less than precise, but this uncertainty is necessary because of the wide
variance in the amount of each chemical needed to have an effect. A substance is generally not
thought of as toxic if it is unreasonable to expect that a person would be exposed to the amount
necessary to cause injury. A susceptible tissue is defined as that part of the body which is
injured after exposure to that particular substance.

Toxic Effects
There have been many attempts to categorize toxic effects and to define them in various ways.
Generally, the terms acute and chronic are used to delineate between effects on the basis of
severity or duration.

The first method or acute exposure is the exposure to a hazardous substance over a short period
of time or at a high dose. A reaction to a chemical can occur at the time of exposure, and might
include vomiting, eye irritation, or other symptoms that often may be readily linked to a
chemical exposure. These are immediate and adverse effects.

The second method or chronic exposure is the exposure to a hazardous substance over a long
period of time. If a carpenter used a stripper regularly and breathed in a little of it 8 hours a day
for 40 years, a chronic exposure would result. This type of exposure occurs when a person is
repeatedly exposed to the same chemical or hazardous substance over a long period of time at
very low levels.

Similarly, the term chronic effect is often used to cover only carcinogenicity, teratogenicity, and
mutagenicity (terms to be discussed below). These effects are obviously a concern in the
workplace, but again do not adequately cover the area of chronic effects, excluding, for example,
blood dyscrasias (such as anemia), chronic bronchitis, and liver atrophy (wasting, losing
function, or size).

Local and Systemic Effects

Local effects from chemical exposure occur at the site of contact, i.e., eye irritation, skin burns or
blistering, respiratory distress, or pulmonary edema. Systemic effects occur at a location distant
from the point of contact, i.e., liver, CNS, heart, or kidneys. These effects may occur years after
a single high level of exposure, or as the result of chronic exposure. Systemic effects are often
more difficult to trace to their cause, and can include organ damage, respiratory diseases, and
other illnesses in an exposed population.

Certain toxic substances produce their long-term effects by altering the genetic code, or DNA,
which tells the bodys cells to perform certain activities. Three categories of effects can result
from such substances:

1. A carcinogenic effect is an increase in an individuals risk of contracting cancer.

(a) It has been evaluated by the International Agency for Research on Cancer (IARC), and
found to be a carcinogen or potential carcinogen; or

(b) It is listed as a carcinogen or potential carcinogen in the Annual Report on Carcinogens

published by the National Toxicology Program (NTP) (latest edition); or

(c) It is regulated by OSHA as a carcinogen.

2. A mutagenic effect is a permanent change in the genetic material (DNA), which may be
passed along to later generations.

3. A teratogenic effect is an increased risk that a developing embryo will have physical defects.

Determining what level of exposure causes these effects requires laboratory research under
controlled conditions. Even then, results must be extrapolated from laboratory animals to
humans. That is, scientists must make assumptions and apply formulas to decide what their
experiments tell them about human exposures.

Another way to classify a hazardous substance or chemical is by their physiological effects. This
classification includes the following major groups:

1. Irritants are chemicals which are not corrosive, but which cause a reversible inflammatory
effect on living tissue by chemical action at the site of contact. A chemical is a skin irritant if,
when tested on the intact skin of albino rabbits by the methods of 16 CFR 1500.41 for 4
hours exposure or by other appropriate techniques, it results in an empirical score of five or
more. A chemical is an eye irritant if so determined under the procedure listed in 16 CFR
1500.42 or other appropriate techniques.

2. Corrosives are chemicals that cause visible destruction of, or irreversible alterations in, living
tissue by chemical action at the site of contact. For example, a chemical is considered to be
corrosive if, when tested on the intact skin of albino rabbits by the method described by the
U.S. Department of Transportation in appendix A to 49 CFR part 173, it destroys or changes
irreversibly the structure of the tissue at the site of contact following an exposure period of 4
hours. This term shall not refer to action on inanimate surfaces.

3. Asphyxiants can be physical or chemical. Physical asphyxiants are gases or vapors that
dilute or displace oxygen normally in the atmosphere. (Vapors from flammable and
combustible liquids displace oxygen in the environment, being heavier than air.) Chemical
asphyxiants are chemicals that prevent the cells from taking up or transferring oxygen in the
body or to the tissues. Carbon monoxide is a well-known asphyxiant, which chemically ties
up the hemoglobin in the blood so that the bodys metabolism slows and stops.

4. Central Nervous System (CNS) Depressants affect the nervous system. This broad category
includes vapors from most anesthetic gases, depressants, and organic solvents (a general
category that includes most household cleaners as well as many paints, glues, and adhesives).
Some CNS depressants produce a feeling of dizziness or giddiness. More severe effects
(including death) can also result.

5. Systemic Toxicants dramatically affect specific organ systems. For example, mercury vapor,
which Victorian hat makers had to inhale regularly when mercury was used in making hats,
causes a serious nervous system disorder which could lead to insanity. (The Mad Hatter in
Alice in Wonderland suffered from an occupational illness.)

6. Sensitizers are chemicals that cause a substantial proportion of exposed people or animals to
develop an allergic reaction in normal tissue after repeated exposure to the chemical.
(Examples are formaldehyde, poison ivy, and poison oak. Some epoxy resins and polyester
resins can cause many people to have a sensitivity reaction and become ill.)

Many chemicals can have multiple effects. For example, xylene, commonly used in paint, is both
an irritant and a CNS depressant.

Symptoms of toxic exposure include a broad range of reactions: chronic coughs, difficulty in
breathing, skin ulcers, diarrhea, irregular heartbeat, headaches, dizziness, chest pain, sore eyes
and skin, difficulty in sleeping, lack of appetite, weight loss, nausea, tremors, and many others.

However, the same symptoms can result from many other causes as well. Tracing a particular
reaction to a specific source can be a challenge to even the most experienced environmental
toxicologists, allergists, and industrial hygiene specialists. This is further complicated by the fact
that many effects are delayed, and are apparent only later in life. The individual experiencing the
symptom may no longer live near the original source, or may not even know that the exposure
occurred.

At low enough exposure levels, a toxic substance will produce no observable harmful effects. As
the dose increases, so does the potential for harm. For every substanceeven table saltthere is
a lethal dose.

HAZARDOUS MATERIALS IN THE ENVIRONMENT

The movement of contaminants within a medium such as air, groundwater, or soil is known as
transport.

Hazardous materials can enter the environment either from a specific source that can be
pinpointed, known as a point source, or from sources that are more spread out, known as area
sources. A factory smokestack and the flow of toxic waste from a pipe to a stream are point
sources, while the liquid runoff from a field in which pesticides were used is considered an area
source.

Contaminants behave differently in the environment depending on their physical state. A solid
may stick to surfaces, scatter, or form a dust cloud; a liquid may seep into the ground, flow along
the ground, or vaporize and become a gas; a gas will expand and be carried by the wind. Some
chemicals are volatile, meaning that they evaporate easily. Such a chemical may enter a stream
as a liquid but rapidly become an air pollution problem.

A non-volatile chemical entering the same stream at the same point may behave quite differently.
A soluble chemical is one that will dissolve readily in water, and would be carried by the stream.
Soluble chemicals tend to be mobile, meaning that they will move rapidly in the ground because
they can be easily dissolved in groundwater. Another chemical might be more likely to adsorb to
soil particles, becoming attached to particle surfaces. Such a chemical would attach to particles
in the stream and eventually settle at the bottom. If the chemical were a persistent one, which
resists breakdown in the environment, it might remain there for some time in the same form,
while bacteria might break down a less persistent chemical. This breakdown is called
biodegradation, and is an important risk management concept. Sometimes it is possible to
increase biodegradation so that materials lose their harmful properties more readily.

The process of chemical breakdown, or biodegradation, can cause materials to lose their
harmful properties and, in effect, disappear.

Certain chemicals tend to become more highly concentrated as they move through the food
chain. This process is known as biomagnification.

Contaminants enter any of the various mediaair, groundwater, surface water, or soiland
move as a mass along with the general flow of that medium. This movement of contaminants
within a medium is called transport. Substances in transport also tend to spread out as they
move, becoming diluted to a varying extent by the medium. This generally reduces the
concentration, and therefore lowers the level of hazard.

Once a toxic substance is released into a medium, a number of different processes can occur:
1. The substance moves in a pathway determined by its own characteristics and those of the
medium that is carrying it.

2. The substance spreads out or disperses, reducing the level of hazard. This means of reducing
risk is not always reliable or consistent, however. For example, there may be periods of low
flow in streams when the volume of water is reduced and less dilution occurs.

3. The material may change chemically or break down into other elements or compounds.
Sometimes a contaminant will combine with another substance to become a more dangerous
chemical; at other times it will be rendered less harmful by the encounter. Some chemicals
have a synergistic effect. (A synergistic effect is the effect of two chemicals acting together
causing a greater effect than the simple sum of their effects when acting alone.)

4. A chemical may also potentiate. (Potentiation is the ability of one or more chemicals to
increase the toxicity of another chemical to cause greater harm than the total effects of the
two expected reactions.) An example is an alcohol. When mixed it will potentiate the effects
of many chlorinated hydrocarbons.

5. The reverse is also possible regarding a chemical. It may present an antagonistic effect. Or
the results of two or more chemicals may lessen the total effects of their combined exposure
in the body. An example might be one taking aspirin to lessen the effects of an alcohol (wine
or beer) exposure from the night before.

6. A toxic substance may move from one medium to another (for example, evaporating from
water into air).

7. Toxic substances can build up in the food chain. Organisms can absorb contaminants such as
pesticides in a process known as bioaccumulation. These contaminants are later released into
another organism that eats that animal or plant. Certain chemicals also tend to become more
concentrated as they move up the food chain. (For example, toxic concentrations may be
higher in a bird that ate insects containing poison than in the insects themselves.) This is
known as biomagnification. Often, an important part of understanding a chemicals risk to
humans is being aware of how a particular contaminant will move through a food chain and
how each animal or plant in the chain may be affected.

The way a pollutant is transformed by chemical reactions and transported through the
environment is called its fate. As we have seen, the fate of chemicals released at the same site
may be extremely different.

The Movement of Contaminants in Different Mediums

Hazardous substances move and disperse differently, depending on the medium in which they
are deposited. Regulators set standards for exposure in each media separately, trying to take the
unique features of each one into account. There are four transport mediums in which
contaminants travel.

Hazardous chemicals can enter the atmosphere from a point source (such as an industrial stack),
or from an area source (such as the evaporation of volatile compounds from hazardous waste
sites). A major factor affecting the level of contaminants in the air is the rate of dispersion, which
is affected by both weather and topography (the shape of the land, including buildings). With a
good, strong wind, air pollutants are dispersed more rapidly; when the air is calm, contaminant
concentration increases. As a rough rule of thumb, contaminant levels are halved when wind
speed is doubled. (This rule of thumb assumes no effect from topographical features.)

Groundwater
Groundwater, defined as water moving through soil and rock, is a common route for chemical
movement. The source of groundwater contamination can include surface impoundments in
which hazardous materials are disposed or stored, such as ponds and lagoons, leaking
underground storage tanks, or any spill where contaminants can seep downward. The type of soil
configuration is crucial in groundwater contamination. Some soil layers, such as clay, are harder
for contaminants to move through (less permeable) and can protect the underlying groundwater.

Surface Water

Surface water includes oceans, rivers, lakes, streams, or any aboveground water source. It may
be contaminated by industrial and sewage discharge pipes, chemical spills, or hazardous waste
landfills.

Soil
Soil may become contaminated through dumping, spills, and other sources. Rainwater leaches
some contaminants from the soil and carries them to the groundwater; other contaminants remain
near the surface, where they can affect human health by entering the food chain (ingestion),
emitting toxic vapors (inhalation), or rubbing onto the skin of children playing in the dirt (dermal
absorption). Because contaminated soil is a basic contaminant medium that affects other media,
it is of considerable importance.
Surface water generally dilutes contaminants as it moves; they tend to break down as they
contact air and light. Contaminants resist breakdown in groundwater and do not disperse
readily because there is nowhere to go.